WO2019218991A1 - 一种新型多元聚丙烯腈共聚物及其纺丝原液的制备方法 - Google Patents

一种新型多元聚丙烯腈共聚物及其纺丝原液的制备方法 Download PDF

Info

Publication number
WO2019218991A1
WO2019218991A1 PCT/CN2019/086772 CN2019086772W WO2019218991A1 WO 2019218991 A1 WO2019218991 A1 WO 2019218991A1 CN 2019086772 W CN2019086772 W CN 2019086772W WO 2019218991 A1 WO2019218991 A1 WO 2019218991A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyacrylonitrile copolymer
spinning dope
novel
preparing
novel polyacrylonitrile
Prior art date
Application number
PCT/CN2019/086772
Other languages
English (en)
French (fr)
Inventor
朱才镇
刘会超
张硕
石逯迪
杨敬龙
于佳立
徐欢
马晨生
王明良
刘瑞刚
徐坚
Original Assignee
深圳大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 深圳大学 filed Critical 深圳大学
Publication of WO2019218991A1 publication Critical patent/WO2019218991A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C08F220/48—Acrylonitrile with nitrogen-containing monomers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent

Definitions

  • the invention belongs to the technical field of high-performance fiber manufacturing, and in particular relates to a novel polyacrylonitrile copolymer and a preparation method thereof.
  • Carbon fiber is a one-dimensional carbon material with carbon content above 90%. It has high strength, high modulus, high temperature resistance, fatigue resistance and thermal conductivity. It is widely used in advanced fields such as aerospace, defense and military, and national economic fields. . There are many types of precursors for the preparation of carbon fibers, of which polyacrylonitrile, viscose and pitch are industrial scale, and the yield of polyacrylonitrile-based carbon fibers accounts for more than 90% of the carbon fiber production.
  • the polyacrylonitrile homopolymer macromolecules there are strong dipole, hydrogen bond interactions among the cyano groups in the polyacrylonitrile homopolymer macromolecules, the macromolecular chains are tightly packed, the crystallinity is high, and the hydrophilicity is poor; the polyacrylonitrile homopolymer
  • the pre-oxidation is carried out by a free radical cyclization mechanism, and the cyclization temperature is high, and the exothermic concentration is concentrated, which easily causes breakage and degradation of the macromolecular chain, and reduces or even fails to obtain high-performance carbon fibers.
  • the invention provides a novel polyacrylonitrile copolymer and a preparation method thereof, and aims to provide a higher hydrophilicity, lower crystallinity and cyclization temperature, milder heat release rate and higher A polyacrylonitrile copolymer having a carbon ratio and a preparation method thereof.
  • the present invention provides a novel polyacrylonitrile copolymer comprising: a main monomer unit acrylonitrile and a comonomer unit vinyl derivative, the structural formula of the vinyl derivative is as shown in the following formula, the main The monomer unit has a mass content of 90 to 99.99%, and the comonomer unit has a mass content of 0.001 to 10%;
  • the invention also provides a preparation method of a novel polyacrylonitrile copolymer spinning dope, comprising the following steps:
  • the present invention has the beneficial effects of the present invention providing a novel polyacrylonitrile copolymer and a method for preparing the same, comprising a main monomer unit acrylonitrile and a comonomer unit vinyl derivative.
  • a novel polyacrylonitrile copolymer having a vinyl derivative as a comonomer it has the effect of increasing the hydrophilicity of polyacrylonitrile, reducing the crystallinity of polyacrylonitrile, and reducing the initiation of cyclization.
  • 1 is a differential scanning calorimetry diagram of a polyacrylonitrile homopolymer and a polyacrylonitrile copolymer provided by an embodiment of the present invention
  • FIG. 2 is a graph showing the thermal weight loss of a polyacrylonitrile homopolymer and a polyacrylonitrile copolymer provided by an embodiment of the present invention.
  • the addition of unsaturated acidic monomers can improve the hydrophilicity of polyacrylonitrile, and the acidic monomers can also have an ionic mechanism. Initiating the cyclization reaction and reducing the activation of the cyclization reaction can control the cyclization reaction, such as common comonomers such as acrylic acid, methacrylic acid and itaconic acid; and the addition of unsaturated ester monomers can utilize the ester group.
  • the large volume effect reduces the cohesive energy of the polyacrylonitrile and improves the permeability of the oxygen, thereby improving the spinnability of the spinning solution. Accordingly, the present invention contemplates a novel polyacrylonitrile copolymer having the advantages of lower cyclization reaction temperature, mild cyclization exotherm rate, and higher carbon yield.
  • the present invention specifically describes a novel polyacrylonitrile copolymer provided by the present invention, comprising: a main monomer unit acrylonitrile and a comonomer unit vinyl derivative, and the vinyl derivative has a structural formula of formula (1).
  • the main monomer unit has a mass content of 90 to 99.99%
  • the comonomer unit has a mass content of 0.001 to 10%;
  • R1, R2, R3 and R4 are one or more combinations of the following structures: single bond, alkylene, oxygen, sulfur, -SO-, -SO2- or -CO-;
  • A1, A2, A3 And A4 is a combination of one or more of the following structures: hydrogen, hydroxy, decyl, amino, cyano, isocyano, thiocyanyl, nitro, carboxy, carbamoyl, amide, thiocarba
  • the initiator azobisisobutyronitrile, the main monomer acrylonitrile, the vinyl derivative comonomer, and the solvent dimethyl sulfoxide were added to a reaction vessel equipped with a condensing and mechanical stirring device.
  • the percentage of raw materials added is: the main monomer acrylonitrile is 98% of the total mass of the monomer, the vinyl derivative comonomer is 2% of the total mass of the monomer, and the initiator azobisisobutyronitrile is the total mass of the monomer. 0.5%, the total mass percentage of the monomer is 20%.
  • the obtained polyacrylonitrile copolymer had a weight average molecular weight of 52,000 and a molecular weight distribution of 3.25.
  • the initiator azobisisobutyronitrile, the main monomer acrylonitrile, the vinyl derivative comonomer, and the solvent dimethyl sulfoxide were added to a reaction vessel equipped with a condensing and mechanical stirring device.
  • the percentage of raw materials added is: the main monomer acrylonitrile is 96% of the total mass of the monomer, the vinyl derivative comonomer is 4% of the total mass of the monomer, and the initiator azobisisobutyronitrile is the total mass of the monomer. 0.5%, the total mass percentage of the monomer is 20%.
  • the obtained polyacrylonitrile copolymer had a weight average molecular weight of 42,000 and a molecular weight distribution of 3.75.
  • the initiator azobisisobutyronitrile, the main monomer acrylonitrile, the vinyl derivative comonomer, and the solvent dimethyl sulfoxide were added to a reaction vessel equipped with a condensing and mechanical stirring device.
  • the percentage of raw materials added is: the main monomer acrylonitrile is 98% of the total mass of the monomer, the vinyl derivative comonomer is 2% of the total mass of the monomer, and the initiator azobisisobutyronitrile is the total mass of the monomer. 0.5%, the total mass percentage of the monomer is 20%.
  • the obtained polyacrylonitrile copolymer had a weight average molecular weight of 106,000 and a molecular weight distribution of 2.34.
  • the initiator azobisisobutyronitrile, the main monomer acrylonitrile, the vinyl derivative comonomer, and the solvent dimethyl sulfoxide were added to a reaction vessel equipped with a condensing and mechanical stirring device.
  • the percentage of raw materials added is: the main monomer acrylonitrile is 98% of the total mass of the monomer, the vinyl derivative comonomer is 2% of the total mass of the monomer, and the initiator azobisisobutyronitrile is the total mass of the monomer. 0.5%, the total mass percentage of the monomer is 20%.
  • the obtained polyacrylonitrile copolymer had a weight average molecular weight of 151,000 and a molecular weight distribution of 2.58.
  • the initiator azobisisobutyronitrile, the main monomer acrylonitrile, the vinyl derivative comonomer, and the solvent dimethyl sulfoxide were added to a reaction vessel equipped with a condensing and mechanical stirring device.
  • the percentage of raw materials added is: the main monomer acrylonitrile is 96% of the total mass of the monomer, the vinyl derivative comonomer is 4% of the total mass of the monomer, and the initiator azobisisobutyronitrile is the total mass of the monomer. 0.5%, the total monomer mass percentage concentration was 23%.
  • the obtained polyacrylonitrile copolymer had a weight average molecular weight of 48,000 and a molecular weight distribution of 4.11.
  • the initiator azobisisobutyronitrile, the main monomer acrylonitrile, the vinyl derivative comonomer, and the solvent dimethyl sulfoxide were added to a reaction vessel equipped with a condensing and mechanical stirring device.
  • the percentage of raw materials added is: the main monomer acrylonitrile is 98% of the total mass of the monomer, the vinyl derivative comonomer is 2% of the total mass of the monomer, and the initiator azobisisobutyronitrile is the total mass of the monomer. 1.0%, the total monomer mass percentage concentration was 23%.
  • the obtained polyacrylonitrile copolymer had a weight average molecular weight of 67,000 and a molecular weight distribution of 1.76.
  • the polyacrylonitrile copolymer provided by the invention has the advantages of improving the hydrophilicity of the polyacrylonitrile, reducing the crystallinity of the polyacrylonitrile, lowering the cyclization starting temperature, relaxing the exothermic rate of the cyclization reaction, and increasing the carbon yield of the carbon fiber. Effect.
  • the prepared polyacrylonitrile copolymer has a lower initial cyclization temperature, a wider exothermic range, and a slower exothermic rate of the cyclization reaction.
  • the thermal stability of the prepared polyacrylonitrile copolymer was improved, and the carbon yield was also improved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

本发明适用于高性能纤维制造技术领域，提供了一种新型多元聚丙烯腈共聚物，包括：主单体单元丙烯腈和共聚单体单元乙烯基衍生物，所述主单体单元的质量含量为90～99.99%，共聚单体单元质量含量为0.001～10%；还提供了一种新型多元聚丙烯腈共聚物纺丝原液的制备方法，包括：将主单体单元丙烯腈、共聚单体单元乙烯基衍生物的一种或多种、反应溶剂和引发剂加入到带有搅拌和冷凝装置的反应容器中，升温到35~80 oC，通氮气或氩气，在氮气或氩气保护下反应预设时间，然后脱除残余单体和气泡，得到纺丝原液。本发明提供的一种新型多元聚丙烯腈共聚物具有较高亲水性、较低结晶度和环化温度、较温和放热速率以及较高的成碳率。

Description

一种新型多元聚丙烯腈共聚物及其纺丝原液的制备方法 技术领域
本发明属于高性能纤维制造技术领域，尤其涉及一种新型多元聚丙烯腈共聚物及其纺丝原液的制备方法。
 背景技术
碳纤维是一种含碳量在90%以上的一维碳材料，其具有高强、高模、耐高温、耐疲劳和导热导电等特性，广泛应用于航空航天、国防军事等尖端领域和国民经济领域。用于制备碳纤维的前驱体有许多种，其中工业规模的有聚丙烯腈、黏胶和沥青，其中聚丙烯腈基碳纤维的产量占到碳纤维产量的90%以上。
但聚丙烯腈均聚物大分子中的氰基之间存在强的偶极、氢键等相互作用，大分子链堆砌紧密，结晶度较高，亲水性较差；聚丙烯腈均聚物的预氧化以自由基环化机理进行，环化温度高，放热集中，易引起大分子链的断裂、降解，降低甚至无法得到高性能的碳纤维。因此，需要在聚合时加入一定的共聚组分，以降低预氧化过程中的反应活化能，促进环化和交联，缓和预氧化放热反应，改善纤维的致密性和均匀性，提高其强度。
 技术问题
存在聚丙烯腈原丝结构差、碳产率低的技术问题。
 技术解决方案
本发明提供一种新型多元聚丙烯腈共聚物及其纺丝原液的制备方法，旨在提供一种具有较高亲水性、较低结晶度和环化温度、较温和放热速率以及较高成碳率的多元聚丙烯腈共聚物及其制备方法。
本发明提供了一种新型多元聚丙烯腈共聚物，包括：主单体单元丙烯腈和共聚单体单元乙烯基衍生物，所述乙烯基衍生物的结构通式如下式所示，所述主单体单元的质量含量为90～99.99%，所述共聚单体单元的质量含量为0.001～10%；
Figure dest_path_image001
。
本发明还提供了一种新型多元聚丙烯腈共聚物纺丝原液的制备方法，包括如下步骤：
将所述主单体单元丙烯腈、所述共聚单体单元乙烯基衍生物的一种或多种、反应溶剂和引发剂加入到带有搅拌和冷凝装置的反应容器中，升温到35~80 oC，通氮气或氩气，在氮气或氩气保护下反应预设时间，然后脱除残余单体和气泡，得到纺丝原液。
有益效果
本发明与现有技术相比，有益效果在于：本发明提供的一种新型多元聚丙烯腈共聚物及其纺丝原液的制备方法，包括主单体单元丙烯腈和共聚单体单元乙烯基衍生物，通过提供这种新型的以乙烯基衍生物为共聚单体的多元聚丙烯腈共聚物，使得其具有提高聚丙烯腈的亲水性，降低聚丙烯腈的结晶度，降低环化起始温度，缓和环化反应放热速率和提高碳纤维的碳产率的效果。
 附图说明
图1是本发明实施例提供的聚丙烯腈均聚物和多元聚丙烯腈共聚物的差示扫描热分析图；
图2是本发明实施例提供的聚丙烯腈均聚物和多元聚丙烯腈共聚物的热失重图。
 本发明的实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
针对现有技术中存在的聚丙烯腈原丝结构差、碳产率低的技术问题，理论上，加入不饱和酸性单体能提高聚丙烯腈的亲水性，酸性单体还可以以离子机理引发环化反应，降低环化反应的活化能使环化反应得到控制，如常见的丙烯酸、甲基丙烯酸和衣康酸等共聚单体；而加入不饱和酯类单体则可以利用酯基较大的体积效应降低聚丙烯腈的内聚能，改善氧的渗透性，从而改善纺丝液的可纺性。因此，本发明设计了一种新型的多元聚丙烯腈共聚物，其具有较低的环化反应温度、温和的环化放热速率和较高碳产率等优点。
下面具体介绍本发明提供的一种新型多元聚丙烯腈共聚物，包括：主单体单元丙烯腈和共聚单体单元乙烯基衍生物，所述乙烯基衍生物的结构通式如式（1）所示，所述主单体单元的质量含量为90～99.99%，共聚单体单元质量含量为0.001～10%；
Figure dest_path_image002
（1）。
其中，R1，R2，R3和R4为下述结构中的一种或多种组合：单键，亚烷基，氧，硫，-SO-，-SO2-或-CO-；A1，A2，A3和A4为下述结构中的一种或多种组合：氢，羟基，巯基，氨基，氰基，异氰基，氰硫基，硝基，羧基，氨基甲酰基，酰胺基，硫代氨基甲酰基，磺酸基，氯磺酰基，卤素或必要时各为取代基的烷基，烷氧基，烷硫基，烷基亚硫酰基，烷基氨基，二烷基氨基，烷氧基羰基，二烷氧基磷酸基，二烷氧基硫酸基，链烯基，链烯基氧，链烯基氨基，亚烷基氨基，链烯基氧羰基，炔基，炔基氧，炔基氨基，炔基氧羰基，环烷基，环烷氧基，环烷基烷基，环烷基烷氧基，环亚烷基氨基，环烷氧基羰基，环烷基烷氧基羰基，芳基，芳氧基，芳基烷基，芳基烷氧基，芳基氧羰基，芳基烷氧基羰基，杂环基，杂化基烷基，杂环基烷氧基，芳基氧羰基，芳基烷氧基羰基，杂环基，杂环基烷基，杂化基烷基，杂环基烷氧基或杂环烷氧基羰基。
下面举具体实施例介绍制作这种纺丝原液的方法：
实施例1：
将引发剂偶氮二异丁腈，主单体丙烯腈，乙烯基衍生物共聚单体，溶剂二甲基亚砜加入到带有冷凝和机械搅拌装置的反应釜中。所加原料百分比为：主单体丙烯腈为单体总质量的98%，乙烯基衍生物共聚单体为单体总质量的2%，引发剂偶氮二异丁腈为单体总质量的0.5%，单体总质量百分比浓度为20%。室温下搅拌混合，通氮气30分钟后，在氮气保护下，60 oC恒温反应8h，然后脱除残余单体和气泡，得到纺丝原液。所得多元聚丙烯腈共聚物的重均分子量为5.2万，分子量分布为3.25。
实施例2：
将引发剂偶氮二异丁腈，主单体丙烯腈，乙烯基衍生物共聚单体，溶剂二甲基亚砜加入到带有冷凝和机械搅拌装置的反应釜中。所加原料百分比为：主单体丙烯腈为单体总质量的96%，乙烯基衍生物共聚单体为单体总质量的4%，引发剂偶氮二异丁腈为单体总质量的0.5%，单体总质量百分比浓度为20%。室温下搅拌混合，通氮气30分钟后，在氮气保护下，60 oC恒温反应8h，然后脱除残余单体和气泡，得到纺丝原液。所得多元聚丙烯腈共聚物的重均分子量为4.2万，分子量分布为3.75。
实施例3：
将引发剂偶氮二异丁腈，主单体丙烯腈，乙烯基衍生物共聚单体，溶剂二甲基亚砜加入到带有冷凝和机械搅拌装置的反应釜中。所加原料百分比为：主单体丙烯腈为单体总质量的98%，乙烯基衍生物共聚单体为单体总质量的2%，引发剂偶氮二异丁腈为单体总质量的0.5%，单体总质量百分比浓度为20%。室温下搅拌混合，通氮气30分钟后，在氮气保护下，60 oC恒温反应12h，然后脱除残余单体和气泡，得到纺丝原液。所得多元聚丙烯腈共聚物的重均分子量为10.6万，分子量分布为2.34。
实施例4：
将引发剂偶氮二异丁腈，主单体丙烯腈，乙烯基衍生物共聚单体，溶剂二甲基亚砜加入到带有冷凝和机械搅拌装置的反应釜中。所加原料百分比为：主单体丙烯腈为单体总质量的98%，乙烯基衍生物共聚单体为单体总质量的2%，引发剂偶氮二异丁腈为单体总质量的0.5%，单体总质量百分比浓度为20%。室温下搅拌混合，通氮气30分钟后，在氮气保护下，60 oC恒温反应24h，然后脱除残余单体和气泡，得到纺丝原液。所得多元聚丙烯腈共聚物的重均分子量为15.1万，分子量分布为2.58。
实施例5：
将引发剂偶氮二异丁腈，主单体丙烯腈，乙烯基衍生物共聚单体，溶剂二甲基亚砜加入到带有冷凝和机械搅拌装置的反应釜中。所加原料百分比为：主单体丙烯腈为单体总质量的96%，乙烯基衍生物共聚单体为单体总质量的4%，引发剂偶氮二异丁腈为单体总质量的0.5%，单体总质量百分比浓度为23%。室温下搅拌混合，通氮气30分钟后，在氮气保护下，60 oC恒温反应8h，然后脱除残余单体和气泡，得到纺丝原液。所得多元聚丙烯腈共聚物的重均分子量为4.8万，分子量分布为4.11。
实施例6：
将引发剂偶氮二异丁腈，主单体丙烯腈，乙烯基衍生物共聚单体，溶剂二甲基亚砜加入到带有冷凝和机械搅拌装置的反应釜中。所加原料百分比为：主单体丙烯腈为单体总质量的98%，乙烯基衍生物共聚单体为单体总质量的2%，引发剂偶氮二异丁腈为单体总质量的1.0%，单体总质量百分比浓度为23%。室温下搅拌混合，通氮气30分钟后，在氮气保护下，60 oC恒温反应24h，然后脱除残余单体和气泡，得到纺丝原液。所得多元聚丙烯腈共聚物的重均分子量为6.7万，分子量分布为1.76。
本发明提供的多元聚丙烯腈共聚物，具有提高聚丙烯腈的亲水性，降低聚丙烯腈的结晶度，降低环化起始温度，缓和环化反应放热速率，提高碳纤维的碳产率的效果。如图1所示，所制备的多元聚丙烯腈共聚物的起始环化温度较低，放热区间增宽，环化反应放热速率缓慢。如图2所示，所制备的多元聚丙烯腈共聚物的热稳定性得到了提高，同时碳产率也得到了提高。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (9)

  1. 一种新型多元聚丙烯腈共聚物，其特征在于，包括：主单体单元丙烯腈和共聚单体单元乙烯基衍生物，所述乙烯基衍生物的结构通式如下式所示，所述主单体单元的质量含量为90～99.99%，所述共聚单体单元的质量含量为0.001～10%；
    Figure dest_path_image001
    。
  2. 如权利要求1所述的新型多元聚丙烯腈共聚物，其特征在于，所述乙烯基衍生物结构中的R1，R2，R3和R4为下述结构中的一种或多种组合：单键，亚烷基，氧，硫，-SO-，-SO2-或-CO-；A1，A2，A3和A4为下述结构中的一种或多种组合：氢，羟基，巯基，氨基，氰基，异氰基，氰硫基，硝基，羧基，氨基甲酰基，酰胺基，硫代氨基甲酰基，磺酸基，氯磺酰基，卤素或必要时各为取代基的烷基，烷氧基，烷硫基，烷基亚硫酰基，烷基氨基，二烷基氨基，烷氧基羰基，二烷氧基磷酸基，二烷氧基硫酸基，链烯基，链烯基氧，链烯基氨基，亚烷基氨基，链烯基氧羰基，炔基，炔基氧，炔基氨基，炔基氧羰基，环烷基，环烷氧基，环烷基烷基，环烷基烷氧基，环亚烷基氨基，环烷氧基羰基，环烷基烷氧基羰基，芳基，芳氧基，芳基烷基，芳基烷氧基，芳基氧羰基，芳基烷氧基羰基，杂环基，杂化基烷基，杂环基烷氧基，芳基氧羰基，芳基烷氧基羰基，杂环基，杂环基烷基，杂化基烷基，杂环基烷氧基或杂环烷氧基羰基。
  3. 一种如权利要求1或2所述的新型多元聚丙烯腈共聚物纺丝原液的制备方法，其特征在于，包括如下步骤：
    将所述主单体单元丙烯腈、所述共聚单体单元乙烯基衍生物的一种或多种、反应溶剂和引发剂加入到带有搅拌和冷凝装置的反应容器中，升温到35~80 oC，通氮气或氩气，在氮气或氩气保护下反应预设时间，然后脱除残余单体和气泡，得到纺丝原液。
  4. 如权利要求3所述的新型多元聚丙烯腈共聚物纺丝原液的制备方法，其特征在于，所述乙烯基衍生物的质量浓度为0.001~10%。
  5. 如权利要求3所述的新型多元聚丙烯腈共聚物纺丝原液的制备方法，其特征在于，所述主单体单元和所述共聚单体单元占溶液总质量百分比浓度优选为5~35%。
  6. 如权利要求3所述的新型多元聚丙烯腈共聚物纺丝原液的制备方法，其特征在于，所述引发剂为偶氮二异丁腈、偶氮二异戊腈、偶氮二异庚腈或偶氮二异丁酸二甲酯，其含量为0.01~5%。
  7. 如权利要求3所述的新型多元聚丙烯腈共聚物纺丝原液的制备方法，其特征在于，所述反应溶剂为二甲基亚砜、二甲基甲酰胺、二甲基乙酰胺或N-乙烯基吡咯烷酮。
  8. 如权利要求3所述的新型多元聚丙烯腈共聚物纺丝原液的制备方法，其特征在于，所述共聚单体单元的加入采用一次加入、分部加入或连续加入的方式。
  9. 如权利要求3所述的新型多元聚丙烯腈共聚物纺丝原液的制备方法，其特征在于，所述预设时间为0.2~24h。
PCT/CN2019/086772 2018-05-17 2019-05-14 一种新型多元聚丙烯腈共聚物及其纺丝原液的制备方法 WO2019218991A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201810474301.6 2018-05-17
CN201810474301.6A CN108586658A (zh) 2018-05-17 2018-05-17 一种新型多元聚丙烯腈共聚物及其纺丝原液的制备方法

Publications (1)

Publication Number Publication Date
WO2019218991A1 true WO2019218991A1 (zh) 2019-11-21

Family

ID=63631607

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/086772 WO2019218991A1 (zh) 2018-05-17 2019-05-14 一种新型多元聚丙烯腈共聚物及其纺丝原液的制备方法

Country Status (2)

Country Link
CN (1) CN108586658A (zh)
WO (1) WO2019218991A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108586658A (zh) * 2018-05-17 2018-09-28 深圳大学 一种新型多元聚丙烯腈共聚物及其纺丝原液的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101158060A (zh) * 2007-11-20 2008-04-09 中国科学院长春应用化学研究所 一种二元丙烯腈共聚物纺丝液及制备方法
CN103014894A (zh) * 2012-12-12 2013-04-03 中国科学院宁波材料技术与工程研究所 一种具有低分子量分布的丙烯腈共聚物纺丝液的制备方法
CN103030736A (zh) * 2012-12-12 2013-04-10 中国科学院宁波材料技术与工程研究所 一种低分子量分布的丙烯腈共聚物纺丝液的制备方法
CN103103631A (zh) * 2013-02-27 2013-05-15 威海拓展纤维有限公司 制备聚丙烯腈碳纤维原丝的方法
CN105085797A (zh) * 2015-08-28 2015-11-25 国网智能电网研究院 一种聚丙烯腈基碳纤维纺丝液及其制备方法
CN108586658A (zh) * 2018-05-17 2018-09-28 深圳大学 一种新型多元聚丙烯腈共聚物及其纺丝原液的制备方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101864028B (zh) * 2010-05-28 2012-05-30 金发科技股份有限公司 一种聚丙烯腈纺丝原液的制备方法
CN105524213B (zh) * 2014-10-27 2018-01-09 中国石油化工股份有限公司 聚丙烯腈纺丝原液的制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101158060A (zh) * 2007-11-20 2008-04-09 中国科学院长春应用化学研究所 一种二元丙烯腈共聚物纺丝液及制备方法
CN103014894A (zh) * 2012-12-12 2013-04-03 中国科学院宁波材料技术与工程研究所 一种具有低分子量分布的丙烯腈共聚物纺丝液的制备方法
CN103030736A (zh) * 2012-12-12 2013-04-10 中国科学院宁波材料技术与工程研究所 一种低分子量分布的丙烯腈共聚物纺丝液的制备方法
CN103103631A (zh) * 2013-02-27 2013-05-15 威海拓展纤维有限公司 制备聚丙烯腈碳纤维原丝的方法
CN105085797A (zh) * 2015-08-28 2015-11-25 国网智能电网研究院 一种聚丙烯腈基碳纤维纺丝液及其制备方法
CN108586658A (zh) * 2018-05-17 2018-09-28 深圳大学 一种新型多元聚丙烯腈共聚物及其纺丝原液的制备方法

Also Published As

Publication number Publication date
CN108586658A (zh) 2018-09-28

Similar Documents

Publication Publication Date Title
WO2018166242A1 (zh) 具有低介电常数和高断裂韧性聚酰亚胺膜的制备方法
CN102041576B (zh) 一种聚酰亚胺纤维及其制备方法
WO2019218991A1 (zh) 一种新型多元聚丙烯腈共聚物及其纺丝原液的制备方法
CN107675283B (zh) 高强芳香族共聚酰胺纤维及其制备方法
CN101831729B (zh) 一种聚丙烯腈基碳纤维的高亲水性和放热性纺丝液及其制备方法
US20210087717A1 (en) Stabilized fiber, method of producing the same, and method of producing carbon fiber
JP2020510746A (ja) 炭素繊維製造用アクリロニトリル系重合体の製造方法
KR101252789B1 (ko) Ｐａｎ계 탄소섬유 프리커서용 아크릴로니트릴계 공중합수지조성물
US20230357959A1 (en) Quad-polymer precursor for producing carbon fiber, method for producing same and method for using same
KR20110125957A (ko) 탄소섬유 성형용 폴리아크릴로나이트릴 공중합체의 제조방법, 이로부터 제조된 폴리아크릴로나이트릴 공중합체 및 이를 이용한 탄소섬유의 제조방법
EP2744859A1 (en) Dry-jet wet spun carbon fibers and processes for making them using a nucleophilic filler/pan precursor
Jamil et al. Redox synthesis and thermal behaviorof acrylonitrile-methyl acrylate-fumaronitrile terpolymer as precursor for carbon fiber
CN1231616C (zh) 制备聚丙烯腈纺丝液的方法
KR102161029B1 (ko) 탄소섬유 제조용 아크릴로니트릴계 중합체의 제조방법
CN1171918C (zh) 一种聚丙烯腈基炭纤维纺丝液的制备方法
CN109137122B (zh) 一种离子液体改性耐热聚丙烯腈纤维的制备方法
KR20110078249A (ko) 탄소섬유용 폴리아크릴로니트릴계 전구체 섬유 제조 방법
US20210230330A1 (en) Acrylonitrile-based copolymer for carbon fiber
KR101276469B1 (ko) 탄소섬유용 폴리아크릴로니트릴계 전구체 섬유의 제조방법
CN105085797A (zh) 一种聚丙烯腈基碳纤维纺丝液及其制备方法
JP2020117634A (ja) 炭素材料前駆体成形体、その製造方法、及びそれを用いた炭素材料の製造方法
KR20120077628A (ko) 탄소섬유 전구체의 제조방법 및 그에 의하여 제조된 탄소섬유 전구체
JP7405727B2 (ja) 炭素材料前駆体、耐炎化炭素材料前駆体の製造方法、及び炭素材料の製造方法
JPWO2019003914A1 (ja) 炭素繊維前駆体繊維の製造方法ならびに炭素繊維の製造方法
JP6471295B2 (ja) 炭素繊維前駆体繊維の製造方法と、炭素繊維の製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19802557

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205 DATED 27/01/2021)

122 Ep: pct application non-entry in european phase

Ref document number: 19802557

Country of ref document: EP

Kind code of ref document: A1